Epoxidized diesters of polyoxyethylene isosorbide



United States Patent 3,225,067 EPOXIDIZED DIESTERS 0F POLYOXYETHYLENE ISOSORBIDE John W. Le Maistre, Claymont, and Ernest C. Ford, .lr.,

Wilmington, Del., assignors to Atlas Chemical Industries, Inc., Wilmington, Del., a corporation of Delaware No Drawing. Filed June 20, 1962, Ser. No. 206,149

3 Claims. (Cl. 260347.4)

This invention relates to new compounds which are plasticizers for vinyl resin and to plasticized vinyl resin compositions, particularly plasticized polyvinyl chloride and copolymers of vinyl chloride and vinyl acetate.

It is an object of this invention to provide novel plasticizers for vinyl resin compositionsv Another object of this invention is to provide epoxidized substances which have superior properties when employed as plasticizers for such plastic materials as vinyl chloride or vinyl chloride and vinyl acetate resins.

Another object is to provide vinyl resin compositions plasticized with plasticizers which contribute markedly to the thermal stability of the composition.

A further object is to provide plasticized vinyl resin compositions of superior low temperature flexibility characteristics.

The above and other objects will become apparent in the course of the following description and the appended claims.

In general, the resin compositions contemplated by the present invention contain a vinyl resin, a stabilizer and a plasticizer. The vinyl resin is selected from the group consisting of vinyl chloride polymers and copolymers of vinyl chloride and vinyl acetate, said copolymers containing not more than about 15% vinyl acetate. Such resins are well known in commerce, and need no further characterization.

Conventional stabilizers for vinyl resins, which may be employed in the compositions of the present invention, are likewise well known in the resin and plastics art. Examples of such conventional stabilizers that are adapted to use in vinyl resin compositions and that are adapted to use in this invention include: alkaline earth-metal soaps, resinates, oxides or carbonates, aromatic amines, epichlorohydrin, organo-tin compounds, epoxidized oils, phenoxypropene oxide and dibutyl laurate.

According to the present invention, plasticizers for vinyl resin are provided which have not heretofore been disclosed in the prior art and vinyl resin compositions are provided which by virtue of the presence of these novel plasticizers have markedly increased thermal stability and superior flexibility at low temperatures.

The plasticizers of the present invention may be described as being diesters of oxyethylated isosorbide and epoxidized fatty acids.

In general, plasticizers of the present invention may be obtained by: (1) reacting an alkylene oxide, for example, ethylene oxide, with isosorbide to form an oxyethylated product; (2) reacting this product with 2 mols of an unsaturated fatty acid to form the diester of the oxyethylated product, and; (3) epoxidizing of unsaturated fatty acid groups of the product of step 2.

Generally, if the number of added alkylene oxide groups falls below about 2, the final resin product produced by the method of this invention will be found to be susceptible to splitting when flexed under conditions of moderately extreme, -65 F., cold. If the number of added alkylene oxide groups is greater than 8, the final product produced by the method of this invention will generally be found to be unsuited to use as a plasticizer because the final resin product exhibits undesirable sensitivity to water. The number of alkylene oxide groups which are "ice reacted with each mol of isosorbide in step (1) above may desirably vary from about 2 to about 8. Preferably, the number of alkylene oxide groups ranges between 3 and 6, within this range the products are eminently suited to use in the invention.

The unsaturated fatty acid suited to use in step (2) and epoxidized in step (3) may beany aliphatic unsaturated fatty acid, for example, oleic, linoleic or linolenic, undecylenic, palmitoleic, erucic, eleostearic and licanic acids. A suitable source of unsaturated fatty acid may be any naturally occurring product that yields such acids such as soya oil, linseed oil, menhaden oil, rapeseed oil, tung oil, oiticica oil and safflower oil. Preferably, the fatty acids suited to use in this invention contain from about 12 to 22 carbon atoms. The heat stability of the final resin product improves as the percent of epoxidation of the unsaturated fatty acid groups in the plasticizer mixture increases. Generally when less than 25% of the olefinic groups in the plasticizer mixture has been epoxidized the final resin product has an undesirably low heat stability. Therefore, preferably at least about 25% of the unsaturation in the plasticizer mixture is epoxidized and as this figure approaches the heat stability is improved.

An example of a plasticizer which has been found eminently satisfactory for use in vinyl resin compositions is polyoxyethylene (4) isosorbide di (9, 10 epoxy stearate). In the foregoing expression, the figure (4) indicates the number of mols of ethylene oxide added to each mol of the compounds.

The proportions of components of the novel plasticized vinyl resin compositions will vary over a considerable range according to the choice of ingredients and the purpose for which the composition is intended. In general, however, useful compositions are obtained by employing from about 15 to about 65% by weight of plasticizer to the total weight of vinyl resin.

For various special purposes to which the compositions may be put, it may be desirable to also incorporate other ingredients such as dyes, fillers, pigments, other plasticiizers, other stabilizers, or other resins either synthetic or natural. For preparing coating compositions various solvents may be used such as alcohols, esters, ketones and hydrocarbons.

The following examples illustrate the preparation and use of the epoxidized substances of this invention:

EXAMPLE I A polyoxyethylene (4) isosorbide starting material was prepared by reacting isosorbide with ethylene oxide. 1200 g. of isosorbide and 5.3 g. of sodium methylate, as a catalyst, were place-d in a two gallon autoclave. The autoclave was sealed and suflicient ethylene oxide led in to increase the pressure to between 40 and 60 p.s.i.g. The mixture was then heated to a temperature of between and C. As the reaction proceeded, additional ethylene oxide was added to maintain the pressure within the 40 to 60 p.s.i.g. range. After 1446 g, of ethylene oxide had been added, which took a period of about 3 /2 hours, the pressure was allowed to reduce to 0 p.s.i.g. The temperatures were maintained for an additional /2 hour and the reaction product, polyoxyethylene (4) isosorbide removed from the autoclave. The product yield was substantially 100%. The hydroxyl number of the product was 364. The polyoxyethylene (4) isosorbide was deodorized by heating at a temperature of 100 C. under a 15 Hg vacuum for 15 minutes.

918 g. (3.26 moles) of oleic acid and 482 g. (1.47 mol) of isosorbide oxyethylated with four mols of ethylene oxide per mol of isosorbide prepared as described in the preceding paragraph, were charged into a flask equipped with a stirrer, thermometer, and a C0 inlet tube. A blanket of C0 (200 cc./min.) was applied and the charge 3 heated to 180-l85 C. over a time interval of 45 minutes.

After heating for 2 hours at 180-185 C., the temperature was raised to 195-200" C. and the reaction allowed to continue until the charge had an acid number of 23. This required 8 hours. The excess oleic acid was then removed by stripping under a vacuum of 1-2 mm. This step required one hour. The charge temperature reaching 215 C. at the end of the stripping operation.

The mass was then cooled to 120 C. and 1% by weight of the charge of active carbon was added. After one hour at 120 C., the mixture was filtered and the product yield was 99% by weight based on the weight of the starting materials. The product was an amber, oily liquid, being polyoxyethylene (4) isosorbide dioleate.

500 g. (1.17 mols unsaturated) of the above diester and 15.1 g. of anhydrous sodium acetate were charged into a flask equipped with a thermometer, a stirrer, a reflux condenser and an additional funnel. The charge was cooled to 20 C. by use of a cold water bath. Over a period of three hours, 232 g. (1.22 mols) of 40% peracetic acid were added, the temperature of the charge being maintained between 20 and 25 C. by means of a cold water bath. After the addition of peracetic acid the charge was held at 2025 C. for 2 hours and then the temperature increased to the 40-45 C. range for a one hour period.

The charge was then cooled to room temperature and transferred into a separatory funnel. 400 cc. of ether and 200 cc. of cold water were added. The mixture was vigorously agitated. Upon standing, an oily layer of product was obtained on top of the acidic water layer. The acidic water layer was then drawn off. Successive 200 cc. cold Water washes were made until a product only faintly acidic was obtained. This product was allowed to stand overnight and after a final separation of water, was transferred to a flask equipped with a stirrer, a thermometer, a distillation head, a condenser and a receiver. The ether and residual water were removed under vacuum.

The final product after filtration was a light colored, amber liquid which had the following analysis: epoxide equiv. 494, acid number 20, saponification number 139, hydroxyl number 23 and bromine number 1.4, and was determined to be substantially polyoxyethylene (4) isosorbide di (9, epoxy stearate).

EXAMPLE II 50 parts by weight of the product of Example I, 100 parts by Weight of polyvinyl chloride, 2 parts by weight of a heat stabilizer, Ferro 1234, a product of Ferro Chemical Corporation, believed to be a metallic salt of a fatty acid such as barium laurate, and 0.5 part by weight of stearic acid as a lubricant were kneaded together until a homogeneous mixture was obtained. The mixture was fed into a roll mill operating at a temperature of approximately 300 F. with a roll clearance of 0.04 inch. The mixture was fiuxed into a sheet, the formed sheet removed from the mill, rotated 90 and again placed in the mill. This procedure was repeated until three passes had been completed. The plastic sheet stock was then allowed to band and the roll clearance adjusted to produce a small rolling bank of material between the rolls. After each minute of banding the stock is cut from each side of the band and added to the bank. After five cuts have been completed, the clearance was adjusted to 0.04 inch and the resultant polyvinyl chloride sheet product removed from the mill.

The heat stability of the product was tested by exposing a portion of the milled sheet product to a temperature of 350 F. for a period of two hours. Although during the test the product changed from a very slightly amber to amber in color no noticeable decomposition was observed.

The cold stiffness property of the product was determined by testing a sample of the milled sheet product in accord with the procedure described in ASTM D1043- 51. In this test a sample of the material to be tested is placed in a clamp and cooled to a low temperature. Torque is then applied to twist the sample out of shape. The torque is then released and the time taken for the sample to return to normal is determined. If the sample returns to normal within 5 seconds, the material is considered flexible at the test temperature. The present product returned to normal shape within 5 seconds when twisted at a temperature of 29 C.

The effect of severe temperature change on the product was tested by exposing a sample of the milled sheet product to a temperature of 300 F. for 150 hours, 350 F. for 2 hours and F. for 24 hours. The sample was then flexed on a /s inch steel mandrel at 65 F. The sample showed no signs of splitting or cracking during the cold flex test.

What is claimed is:

1. An epoxidized diester of a polyoxyethylene isosorbide containing from 2 to 8 oxyethylene groups per mol and two mols of an ethylenically unsaturated fatty acid wherein at least 25% of the unsaturation is converted to epoxide groups.

2. A substantially completely epoxidized diester of a polyoxyethylene isosorbide containing from 2 to 8 oxyethylene groups per mol and two mols of an ethylenically unsaturated fatty acid.

3. Polyoxyethylene (4) isosorbide di (9, 10 epoxy stearate).

References Cited by the Examiner UNITED STATES PATENTS 2,766,260 10/1956 Kartinos 260347.4 2,771,471 11/1956 De Groote 260347.4 2,889,300 6/1959 DaZZi 260--30.4 3,020,253 2/1962 Lukes 26030.4

NICHOLAS S. RIZZO, Primary Examiner.

MORRIS LIEBMAN, JOHN D. RANDOLPH,

Examiners. 

1. AN EPOXIDIZED DIESTER OF A POLYOXYETHYLENE ISOSORBIDE CONTAINING FROM 2 TO 8 OXYETHYLENE GROUPS PER MOL AND TWO MOLS OF AN ETHYLENICALLY UNSATURATED FATTY ACID WHEREIN AT LEAST 25% OF THE UNSATURATION IS CONVERTED TO EPOXIDE GROUPS. 